CN109989070B - Three-dimensional grading FeP nanosheet hydrogen evolution electro-catalytic material and preparation method and application thereof - Google Patents
Three-dimensional grading FeP nanosheet hydrogen evolution electro-catalytic material and preparation method and application thereof Download PDFInfo
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- 239000002135 nanosheet Substances 0.000 title claims description 43
- 239000000463 material Substances 0.000 title claims description 19
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims description 18
- 239000001257 hydrogen Substances 0.000 title claims description 18
- 229910052739 hydrogen Inorganic materials 0.000 title claims description 18
- 238000002360 preparation method Methods 0.000 title claims description 7
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 24
- VAKIVKMUBMZANL-UHFFFAOYSA-N iron phosphide Chemical compound P.[Fe].[Fe].[Fe] VAKIVKMUBMZANL-UHFFFAOYSA-N 0.000 claims description 23
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 239000000843 powder Substances 0.000 claims description 14
- 239000013078 crystal Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 229910052742 iron Inorganic materials 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 229910021205 NaH2PO2 Inorganic materials 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000012300 argon atmosphere Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000011144 upstream manufacturing Methods 0.000 claims description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 2
- 239000012159 carrier gas Substances 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 230000002378 acidificating effect Effects 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 229910001868 water Inorganic materials 0.000 description 11
- 230000000694 effects Effects 0.000 description 7
- 239000010411 electrocatalyst Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
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- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910021397 glassy carbon Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002055 nanoplate Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- 229910006297 γ-Fe2O3 Inorganic materials 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- -1 platinum group metals Chemical class 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
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Abstract
本发明涉及一种三维分级FeP纳米片析氢电催化材料及其制备方法和应用，属于电催化析氢领域。本发明首先采用交流电压剥离铁丝制备三维纳米片铁氧化物，作为前驱体；再以次亚磷酸钠晶体为磷源，在石英管式炉中，一步热处理反应制备三维FeP纳米片析氢电催化材料。本发明提供的方法中三维纳米片铁氧化物制备工艺简单、绿色，产率高；采用简便、温和的一步低温磷化法制备三维FeP纳米片析氢电催化材料，成本低、重复性高、易于大规模合成。三维FeP纳米片材料用于电催化析氢反应时表现出优异的催化性能，得到还原电流密度10mA·cm–2时，仅需测试过电位88mV，而塔菲尔斜率仅为47.7mV·dec–1；具有良好的电催化稳定性。
The invention relates to a three-dimensional hierarchical FeP nanosheet hydrogen evolution electrocatalytic material, a preparation method and application thereof, and belongs to the field of electrocatalytic hydrogen evolution. In the present invention, three-dimensional nano-sheet iron oxide is prepared by stripping iron wire with alternating current voltage, which is used as a precursor; then sodium hypophosphite crystal is used as a phosphorus source, and three-dimensional FeP nano-sheet hydrogen evolution electrocatalytic material is prepared by one-step heat treatment reaction in a quartz tube furnace. . In the method provided by the invention, the preparation process of the three-dimensional nano-sheet iron oxide is simple, green, and has high yield; the three-dimensional FeP nano-sheet hydrogen evolution electrocatalytic material is prepared by a simple and mild one-step low-temperature phosphating method, and the cost is low, the repeatability is high, and it is easy to Large-scale synthesis. The three-dimensional FeP nanosheet material exhibits excellent catalytic performance when used in electrocatalytic hydrogen evolution reaction. When the reduction current density is 10 mA·cm –2 , only the test overpotential is 88mV, and the Tafel slope is only 47.7mV·dec –1 ; has good electrocatalytic stability.
Description
Technical Field
The invention belongs to the field of electrocatalytic hydrogen evolution, and particularly relates to a three-dimensional graded FeP nanosheet hydrogen evolution electrocatalytic material as well as a preparation method and application thereof.
Background
With the continuous development of social economy, the energy consumption is increased in a leap-type manner. At present, the energy consumption of China still mainly utilizes non-renewable fossil fuels, and meanwhile, serious environmental pollution and greenhouse effect are brought. In order to cope with the gradual depletion of fossil fuels and the environmental problems caused by the depletion, an environment-friendly and renewable energy production mode is urgently sought.
As the cleanest energy carrier, hydrogen also has the characteristics of high energy density and reproducibility, and can be used as a novel fuel for replacing fossil fuels. The method for preparing hydrogen by electrolyzing water is considered to be an ideal sustainable energy production mode due to the advantages of simple equipment, relatively mature technology, high product purity, no pollution in the process and the like. A huge bottleneck exists in the water electrolysis industry, namely the electric energy consumption is large due to the over-high hydrogen evolution potential of the electrolysis electrode. Therefore, the development of a high-activity catalyst capable of effectively reducing the overpotential of hydrogen evolution of the cathode becomes a challenge and an urgent task for researchers in various countries.
At present, for the hydrogen evolution reaction process, the platinum group noble metal has the best electrocatalytic activity, but the platinum group noble metal has limited storage capacity on the earth, is very expensive, is easy to run off in the reaction process, and is not beneficial to realizing large-scale popularization. Therefore, the search for the elements which are efficient and rich in resources on the earth to replace platinum group metals to prepare cheap and durable non-platinum hydrogen evolution catalytic materials is vital to promote the development of the electrocatalytic hydrogen production technology.
Disclosure of Invention
The invention aims to provide a three-dimensional iron phosphide nanosheet material, and a preparation method and application thereof.
The invention provides a preparation method of a three-dimensional iron phosphide nanosheet material, which specifically comprises the following steps:
(1) soaking an iron material serving as an electrode into NaOH aqueous solution, and applying alternating voltage to the electrode to obtain aqueous solution containing reddish brown suspended matters;
(2) separating solid substances in the water solution containing the reddish brown suspended matters, washing and drying to obtain three-dimensional iron oxide nanosheets;
(3) three-dimensional iron oxide nanosheets and NaH2PO2·H2O crystal powder is respectively placed in two separated positions in a tube furnace, wherein NaH2PO2·H2And (3) taking O crystal powder as an upstream, and taking inert gas (such as argon) as carrier gas to perform heating and phosphorization reaction under the program setting of a tube furnace to obtain black three-dimensional iron phosphide nanosheet material.
Preferably, the ferrous material is iron wire.
Preferably, the concentration of the NaOH aqueous solution is 2-4 mol.L–1。
Preferably, the value of the alternating voltage is 7-10V, and the time for applying the alternating voltage is 1 h.
Preferably, the three-dimensional iron oxide nanosheets and NaH2PO2·H2The mass ratio of the O crystal powder is 1: 10.
Preferably, the program setting parameters of the tube furnace are as follows: at 2 ℃ min–1The temperature rising rate is increased from room temperature to 250-350 ℃, then the temperature is kept for 2-3 hours, and finally the natural cooling is carried out.
The three-dimensional iron phosphide nanosheet material provided by the invention is prepared by adopting the method. The three-dimensional iron phosphide nanosheet material can be used as an electrocatalyst for the electro-decomposition water-out hydrogen reaction.
Compared with the prior art, the invention has the following advantages:
(1) the three-dimensional nano-sheet iron oxide can be continuously generated at room temperature by treating the metal iron wire through the alternating voltage, the method has the advantages of simple required equipment, quick material formation, mild preparation conditions and low price of used materials;
(2) the alternating voltage method is only carried out in blank NaOH base solution, and a three-dimensional nanosheet structure can be generated without a precursor solution and a hard template, so that the method is very simple and green;
(3)NaH2PO2·H2o as phosphorus source, and generating reducing gas PH under low temperature heating3Reducing the three-dimensional nanosheet iron oxide into three-dimensional nanosheet iron phosphide, wherein the three-dimensional nanosheet structure is very stable;
(4) the three-dimensional nanosheet iron phosphide prepared by the method has huge surface area, tearing edges and abundant active sites on the nanosheets owned by folds and a large number of porous channels in hierarchical structures, which are very beneficial to surface reaction and mass transfer;
(5) the novel three-dimensional FeP nanosheet shows high-efficiency activity when being applied to electrolytic water hydrogen evolution reaction, and particularly has the activity of 10mA cm–2Very low overpotential (88 m)V), Small Tafel slope (47.7mV dec)–1) And satisfactory long-term stability.
Drawings
Fig. 1 is an XRD pattern of three-dimensional iron oxide nanoplates of step (1) of example 1.
Fig. 2 is an SEM image of three-dimensional iron oxide nanoplates of step (1) of example 1.
Fig. 3 is an XRD pattern of three-dimensional iron phosphide nanosheets of step (2) of example 1.
Fig. 4 is an SEM image of three-dimensional iron phosphide nanosheets of step (2) of example 1.
FIG. 5 shows that the three-dimensional iron phosphide nanosheets of example 2 are 0.5 mol.L as electrocatalysts–1H2SO4Linear sweep voltammetric polarization curves of (1).
Fig. 6 is a tafel slope curve fitted from a polarization curve using the three-dimensional iron phosphide nanosheets of example 2 as an electrocatalyst.
FIG. 7 shows three-dimensional iron phosphide nanosheets of example 2 as electrocatalysts at a constant temperature of 40mA cm–1Chronopotentiometric curve at current density.
Detailed Description
The surface appearance of the product prepared by the invention is measured by a Scanning Electron Microscope (SEM), the crystal structure of the material is measured by an X-ray diffractometer (XRD), and the catalytic activity of water electrolysis and hydrogen evolution is measured on a Shanghai Chenghua electrochemical workstation.
Example 1
(1) Preparing three-dimensional iron oxide nanosheets:
ultrasonically cleaning two iron wires (2cm long and 0.5mm in diameter) in acetone, absolute ethyl alcohol and deionized water for 20 min; immersing the dried iron wires into 4M NaOH aqueous solution in parallel for 0.5cm, and keeping the distance between the iron wires to be 1.5 cm; applying 8V alternating voltage to the two iron wires, and keeping the solution magnetically stirred for 60 min; collecting suspended matters in the electrolyte by centrifugation, and alternately cleaning the suspended matters with deionized water and absolute ethyl alcohol for 6 times, wherein the rotating speed of a centrifuge is 8000rpm, and the time of each time is 5 min; and (3) drying the cleaned product in an oven at 70 ℃ for 12h to obtain the three-dimensional iron oxide nanosheet.
In FIG. 1X-ray powder diffraction (XRD) analysis revealed that all diffraction peaks of the electrochemically stripped product from iron wire using an 8V AC voltage were ascribed to maghemite crystalline phase, tetragonal gamma-Fe2O3(JCPDS No. 25-1402), no other diffraction peaks were detected, indicating high purity of the resulting sample. Scanning Electron micrographs (see FIG. 2) show that these gamma-Fe2O3The product has a three-dimensional hierarchical continuous microstructure and is formed by cross-assembling a large number of two-dimensional smooth nanosheets (with the thickness of about 10nm) with uneven sizes and tearing-shaped wrinkle edges.
(2) Preparing three-dimensional iron phosphide nanosheets:
mixing the three-dimensional iron oxide nanosheet prepared in the step (1) with NaH2PO2·H2O crystal powder is put in two separated positions of a quartz tube furnace, NaH2PO2·H2O crystal powder is positioned at the upstream, and the mass ratio of the O crystal powder to the O crystal powder is 1: 10; subsequently, the atmosphere in the quartz tube was maintained at a high purity argon atmosphere, and the temperature raising program was set at 2 ℃ for min–1Raising the temperature from room temperature to 350 ℃, keeping the temperature for 120min, and continuously naturally cooling to room temperature under the argon atmosphere after heating; finally, a large number of black three-dimensional iron phosphide nanosheets were collected.
XRD analysis in FIG. 3 shows that upon low temperature phosphating, the maghemite phase Fe2O3The diffraction peak of (B) was completely disappeared and completely converted into orthorhombic FeP (JCPDS No. 89-2746). Meanwhile, the synthesized FeP also has a three-dimensional nanosheet structure (see FIG. 4). Phosphide FeP and its precursor Fe2O3The morphology of (a) is slightly different in that the smooth nanosheets expand and thicken, and many compact tiny nodules appear on the surface.
Example 2
And (3) testing the performance of the three-dimensional iron phosphide nanosheet as the catalyst for the electrolytic water hydrogen evolution reaction:
(1) preparing an electrocatalyst working electrode:
adding 5mg of three-dimensional iron phosphide nanosheet powder and 50 mul of 5 wt% nafion solution into 950 mul of ethanol, and carrying out ultrasonic treatment for 15 min; adding 1.5mg of carbon black powder into the mixed solution, and continuing performing ultrasonic treatment for 30min to form uniform catalyst ink; 5 mul of catalyst ink is transferred and coated on the surface of a glassy carbon electrode (with the diameter of 3mm), and the surface is naturally dried to be tested.
(2) Electrochemical performance study:
the electrochemical properties of the prepared samples were tested on the CHI 660E electrochemical workstation (chenhua instrument, shanghai, china). A traditional three-electrode system, namely a Pt sheet electrode as a counter electrode, a Saturated Calomel Electrode (SCE) as a reference electrode and a catalyst modified glassy carbon electrode as a working electrode is used. 0.5 mol. L–1H2SO4The aqueous solution serves as a supporting electrolyte. Unless otherwise indicated, all potentials in the tests were converted to Reversible Hydrogen Electrode (RHE) potentials according to the nernst equation.
FIG. 5 shows that the three-dimensional iron phosphide nanosheet is 0.5 mol.L as an electrocatalyst–1H2SO4Linear sweep voltammetric polarization curves of (1). The figure shows that the three-dimensional iron phosphide nanosheet has good electrocatalytic activity, and the electrocatalytic decomposition water reaction initial overpotential (defined as the obtained current density of-1 mA-cm)–2Overpotential of) is only 39mV, resulting in-10 mA cm–2The reference current density (equivalent to the current density produced by a 12.3% efficient solar water splitting plant) only needs 88 mV.
FIG. 6 is a Tafel slope curve of three-dimensional iron phosphide nanosheets as an electrocatalyst. The figure shows that the three-dimensional iron phosphide nanosheet has a lower Tafel slope (only 47.7mV dec)–1) The slope is-120 mV · dec–1The interval shows that the mechanism of the catalytic hydrogen evolution reaction is a Volmer-Heyrovsky catalytic mechanism, namely the mechanism consists of a rapid electrochemical reaction step and a slow electrochemical desorption step, and the electrochemical desorption step is a rate control step.
FIG. 7 shows that three-dimensional iron phosphide nanosheets are used as electrocatalysts at 40 mA-cm–1Chronopotentiometric curve at current density. At constant current density (40mA cm)–1) During the continuous test for 20 hours, the overpotential only needs to be applied not more than 145mV, reflecting that the material has high electrocatalytic activity and stability in an acid electrolyte.
Claims (5)
1. A preparation method of a three-dimensional iron phosphide nanosheet material for high-current-stability hydrogen production in an acidic medium is characterized by comprising the following steps:
1) immersing an iron material serving as an electrode into NaOH aqueous solution, applying alternating voltage on the electrode, centrifugally washing and drying the formed reddish brown suspended matters to obtain three-dimensional iron oxide nanosheets;
2) three-dimensional iron oxide nanosheets and NaH2PO2·H2O crystal powder is respectively placed in two separated positions in a tube furnace, wherein NaH2PO2·H2And (3) enabling the O crystal powder to be located at the upstream, enabling the O crystal powder and the O crystal powder to be in a mass ratio of 1:10, and carrying out heating and phosphorization reaction under the program setting of a tubular furnace by taking a high-purity argon atmosphere as a carrier gas to obtain the black three-dimensional iron phosphide nanosheet material.
2. The method of claim 1, wherein the ferrous material is iron wire.
3. The method according to claim 1, wherein the concentration of the NaOH aqueous solution is 2-4 mol-L–1。
4. The method according to claim 1, wherein the AC voltage is 7-10V and the AC voltage is applied for 1 h.
5. The method of claim 1, wherein the tube furnace is programmed with the following parameters: at 2 ℃ min–1The temperature rising rate is increased from room temperature to 250-350 ℃, then the temperature is kept for 2-3 hours, and finally the natural cooling is carried out.
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